Synthetic drying oils



United States PatentO 2,918,440 SYNTHETIC DRYING oILs Alexander M.Partansky, Concord, Califl, assignor to The Dow Chemical Company,Midland, Mich., a corporation of Delaware No Drawing. ApplicationJanuary 26, 1956 Serial No. 561,660

14 Claims. 01. 260-19) This invention has reference to improved,synthetic drying esters having an oily consistency which are especiallysuited for providing superior protective film coatings of the typeordinarily obtained with conventional oleoresinous varnishes.

Varnishes, according to the usual traditional conception and practice,are solutions of natural or synthetic resins in drying oils. Theirpreparation ordinarily involyes cooking the resin together with anunsaturated glyceride, or drying oil until a uniform solution isobtained having more body than the original oil and which thereby isadapted to form harder films on drying. For purposes of obtaining moreuniform compositions that would provide films having bettercharacteristics and improved performance as a protective coating, itwould be advantageous for the bodying and hardening substance of avarnish-like vehicle to be in molecular combination with the unsaturatedfatty acid chains which dry under 'the influence of atmospheric oxygen,instead of being in the mere physical association provided for by theconventional varnish solutions.

It is, therefore, among the principal objects of the present inventionto provide improved synthetic drying oils wherein the resinousconstituent is in chemical comof a phenolformaldehyde novolak resinwherein styrene oxide constitutes at least a portion of the etherifyingsubstituent. It is a primary object of the present invention to providesuch synthetic drying oils as are the drying oil fatty acidesterification products of certain poly-(aryl hydroxy alkylene ethers)and mixed poly-(aryl hydroxy alkylene and hydroxy alkyl ethers) ofnovolaks (herein referred to as polyalcohols or resinous polyalcohols)which are at least partially etherified with styrene oxide 7 and whichadvantageously are based essentially on the common, tri-functionalphenol, C H OH. Additional objects and advantages will be apparentthroughout the following description and specification.

According to the present invention, an improved synthetic drying oil iscomprised of the esterification product of (1) a resinous polyalcoholconsisting of the etherified product of a phenol-formaldehyde novolakwhich is based essentially on the common, tri-functional phenol, C H OH,and which has from three to ten phenolic units per molecule in which atleast a portion of the phenolic hydroxide groups originally present inthe molecule are etherified with styrene oxide and (2) carboxylic acidsin an amount to provide from about 0.2 to 1.0 and preferably in theneighborhood of about 0.5 carboxyl groups per alcoholic hydroxyl of saidresinous polyalcohol, the preponderant amount of such acids being dryingoil fatty acids. Advantageously the resinous polyalcohol which isphenol-formaldehyde novolak of the indicated type with styrene oxide asthe sole etherifying agent in which at least about percent andpreferably all of the phenolic hydroxyl groups originally present in thenovolak are etherified with from about 0.7 to 1.2 and preferably atleast about 0.8 moles of styrene oxide per phenolic unit.Advantageously, for many purposes, the resinous polyalcohol consists ofthe etherified product of a phenolformaldehyde novolak of the indicatedtype with a mixture of etherifying agents consisting of styrene oxideand a relatively more reactive organic oxide selected from the group oforganic epoxides consisting of alkylene oxides containing from 2 to 3carbon atoms in their molecule; hydroxy alkylene oxides containing from3 to 5 carbon atoms in their molecule; and aryl glycidyl ethers in whichat least about 70 percent and preferably all of the phenolic hydroxylgroups originally present in the novolak are etherified with from about0.2 to 1.0 moles of styrene ously from about 1.0 to 0.2, moles of therelatively more polyalcohol is etherified with about 0.5 mole of styreneoxide and a total of not more than about 1.25 moles of both oxides perphenolic unit.

If desired, the improved synthetic drying oil may consist of mixtures ofesterified products of different resinous polyalcohols one ofthe'polyalcohols being independently I etherified solely with styreneoxide and the other being a resinous polyalcohol which may be partiallyetherified with styrene oxide and with the more reactive oxide or whichmay be' completely etherified with the more reactive. organic oxide. Insuch cases it is advantageous for both of the polyalcohols to beetherified with not more the proportion of etherified styreneoxideadducts to the 'sum total of etherified oxide adducts which arepresent in such a mixture to be between about 25 and mol percent.

Preferably, the resinous polyalcohols which are esterified in thepractice of the present invention are prepared from any novolak havingthe indicated molecular characteristics which is based on formaldehydeand, advantag'eously, the common phenol, C H OH, regardless of theparticular method which is employed for its manufacture. Thus, thenovolak may be made under reflux conditions at atmospheric pressure, inthe conventional manner, or it may be made at elevated temperatures andpressures, particularly according to the procedure described in thecopending applications Serial Nos. 382,851 and 382,852, both filedSeptember 28, 1953, in both of which the present inventor is acoapplicant. The optimum molecular ratio of aldehyde to phenol which maybe employed in manufacturing the novolaks varies somewhat with theparticular method which isxutilized. Generally the ratio falls betweenabout 0.65 and 0.95 mole of aldehyde per mole of phenol with greateradvantages being frequently obtainable when the ratio is between about0.75 and 0.85. Usually the novolaks may be prepared by condensing thealdehyde and phenol in the presence of an acid catalyst, such asphosphoric oxalic,

hydrochloric or sulfuric acids. Sometimes, however, useful products maybe obtained from alkali-catalyzed condensations.

Novolaks prepared from the common phenol, C H OH, may generally beemployed with greater advantage for reasons of economy and availabilityand also because of the difficulties, due to steric hindrance, which maybe encountered when novolaks from certain substituted phenolsareemployed and attempted to be etherified with esterifiedniay consist ofthe etherified product of a styrene oxide. As will be illustrated,novolaks prepared fromcertain substituted phenols are not asadvantageous- 1y employed. However, novolaks having minor amounts withcombinations of etherifying agents consisting of styrene oxide and arelatively more reactive organic oxide selected from the group oforganic epoxides consisting of alkylene oxides containing from 2 to 4carbon atoms in their molecule; hydroxy alkylene oxides containing from3 to 5 carbon atoms in their molecule; and aryl glycidyl ethers.Preferably the more reactive oxide is ethylene oxide, propylene oxide orphenyl glycidyl ether. Advantageously, as mentioned, the polyalcohol hasat least about 70 percent, and, more advantageously, has substantiallyall, of the phenolic hydroxyl groups originally present in the novolaketherified by the oxide or oxides employed.

Generally, when superior results are desired, particularly with respectto the caustic resistance of films formed fromthe esterified polyalcoholadducts, the polyalcohol may be etherified with not more than a total ofabout 1.25 moles of both oxides per phenolic unit in which most of theetherifying oxide is styrene oxide. However, in many cases, suitable andmore economical films may be obtained when lesser amounts of styreneoxide areemployed, especially if outstanding caustic resistance in thefilm is not an essential requirement. Ordinarily the partialetherification of the novolak with ethylene oxide or another morereactive oxide produces a resinous polyalcohol having a relatively lowerhydroxyl equivalent weight than when styrene oxide is the sole orpredominant etherifying agent. This facilitates the esterification ofthe polyalcohol by allowing greater amounts of the fatty acids to beemployed in completing the esterification and may be advantageouswhenever an unusually great caustic resistance is not required. Usually,relatively more rugged and chemically inert coatings may be obtainedwhen ethylene oxide is employed as the more reactive oxide in theresinous polyalcohol. Polyalcohols etheritied with styrene oxide alonemay advantageously be in accordance with the disclosure contained in thecopending application of Alexander M. Partansky and Paul G. Schrader,Serial No. 561,684, concurrently filed January 26, 1956. Polyalcoholswhich are partially etherified with styrene oxide and then finished witha more reactive oxide may advantageously be in accordance with thedisclosure contained in the copending application of the same inventorshaving Serial No. 561,683, concurrently filed January 26, 1956.

' Improved synthetic drying oils in accordance with the presentinvention may be obtained by cooking or heating the resinouspolyalcohols having the described characteristics with drying oil fattyacids at temperatures in the neighborhood of about 235240 C. The amountof acid used should be enough to yield an oil soluble ester. This resultmay be obtained by esterifying as little as 0.2 of the hydroxyl groupswhich are available in the resinous polyalcohol. However, the amount ofacid may be enough to esterify substantially all of the hydroxyl groups.Frequently, films having improved caustic resistance may be obtained byemploying relatively less fatty acids for esterification, as whenbetween about 0.4 and 0.6 carboxy groups, i.e., in the neighborhoodofabout 0.5 carboxy groups, are provided by the oil fatty acid peralcoholic hydroxyl present in the polyalcohol.

The preponderant proportion of the acids should be those monomeric acidswhich may be obtained by saponification of drying oils or semi-dryingoils. Relatively small amounts of dicarboxylic acids or theiranhydrides, such as phthalic acid or its isomers, succinic acid, ormaleic anhydride, or dimeric drying oil acids, may be added to theester-producing cook to elfect part of the esterification and toincrease the viscosity of the product. Such materials should not be inexcess of about 40 percent of the carboxy] values present. Theygenerally will not represent more than about 20 percent of the number ofesterifying carboxyl groups present in the total amount of acids used.If their use is especially desirable for any particular reason, it isfrequently preferably to employ them in an amount which constitutes lessthan about 10 percent of the total carboxylic groups employed.

The esterification of the polyalcohols described proceeds in rapidfashion. Generally, acid numbers less than 10 or 15 are obtained withincooking periods of from about 2 to 10 hours, although certain exceptionsmay occur. In certain instances, as, for example, when an excessivebuild up of viscosity is encountered and yet a low acid number isdesired in the finished composition, it may be advantageous to terminatethe esterification towards the end of the reaction by adding arelatively fast reacting polyhydroxy compound, such as glycerol or otherglycols and the like or even a relatively more reactive polyalcoholadduct which has been essentially etherified, for example, with ethyleneoxide, in order to react with any of the unreacted acid that may bepresent. This facilitates obtaining a lower, more desirable, residualacid content in the ester oil product and causes no apparent adverseeffect on the film coatings obtained from such products. As a matter offact, such technique conveniently provides a means for extending thedrying esters with other components of conventional oleoresinousvehicles.

Because of the stability of the improved synthetic drying oils of thepresent invention, and their freedom from tendencies to form gels, theester product can often be safely cooked for longer periods of time ifit is desired to effect some heat bodying after substantial completionof the esterification. The time-viscosity curve which is obtainable frommeasurements of the viscosity of the esterifying product during theperiod of its cooking, does not ordinarily turn sharply toward aposition parallel to the viscosity axis, as in the case of materialswhich tend to gel during cooking. This feature is of salient importancein varnish making, since it permits eater latitude in the preparation ofthe product.

As indicated, satisfactory oils can also be obtained by mixing orblending separately prepared ester products to a desired composition.Alternatively, they can be obtained, as will be illustrated, byesterifying suitable mixtures of pure or different polyalcohols, as, forexample, a mixture of a styrene-oxide etherified resinous polyalcoholand an ethylene or propylene or other desired oxide etherifiedpolyalcohol, in which styrene oxide may or may not have been employedfor the etherification. When this is practiced, it is advantageous forboth of the polyalcohols to be etherified with not more than about 1.25moles of oxide per phenolic unit and for the proportion of etherifiedstyrene oxide adducts to the sum total of etherified oxide adducts whichare present in the esterified product to be between about 25 and molpercent.

The ester products may be employed without modification as clear,varnish-like protective coatings having unusually good causticresistance and other desirable characteristics. Or they may be blendedor cooked with such standard coating constituents as drying oils andalkyl phenolic or other type resins. If desired, they may be prepared aspigmented compositions to prepare coatings having desired colorations.Conventional driers may advantageously be employed to accelerate theirdrying. The compositions provide useful coatingsv either when they areair-dried or baked on desired surfaces.

. in: P actice of; the-present.inventionlis illustrated in .t-andbythe-followingexamples.

' EXAMPLEI ,gA novolak was prepared fromcommon phenol with about 0.82mole of formaldehyde .per mole of phenol in the'presence of about 0.7percent by weight of sulfuric acid, based on the weight ofthe phenol,andwater in ,1 an amount by weight equal -to theamount of phenol. Thereaction was conducted in a Pfaudler reactor at elei yated temperaturesand pressures according to the procedure set forth :in copendingapplication Serial No. 382,852, filed. September 28,1953. After beingneutr-alized, purified and dried, about 500 grams of the now- Ilak wasdissolved in about. 250. grams of dioxane to -which was added aboutgrams of an aqueous solution .vofrcaustic soda containingabout 5.0percent by weight ofi NaOH. The mixture was placed in a high pressure,rocking-type laboratory reactor and slowly heated until -,a steadytemperature of about 115 C. was attained. At thispoint, about 625 gramsof styrene-oxide, which constituted about 1.1 moles of the oxide perhydroxyl equivalent of the no'volak, was added. The reactants weremaintained at a temperature between about 110 and 120 C. while beingheated for a period of about 65 hours', after which the reaction masswas cooled, neutralized with citric acid, devolatilized to free thepolyalcohol from solvent and unreacted styrene oxide, washed with hotwater and dried. There was obtained a practically quantitative yieldconsisting of about 1076 grams of a resinous polyalcohol having amolecular weight of aboutl455 and an equivalent weight of about 225grams per alcoholic hydroxyl group. This is the exact theoretfi'calvalue and indicates that a 100 percent etherification '1 had occurredwithout by-product formation.

An ester was prepared with the polyalcohol by cooki'ng together about198 grams of the polyalcohol and about 126 grams of linseed 'oil fattyacids under a nitrofor a reaction period of about 36- hours.

. table also includes details relating tO-xthfl alcohol and soya oilfatty acids.

EXAMPLE II A novolak having a molecular-weight of about 800 was preparedina pressure vessel by reacting, at 150 C. for one hour, about 8235grams of common phenol with about 5900 grams of formalin (to provide analdehyde to phenol ratio of about 0.82) .in the presence ofabout 8590milliliters of supplementarywater and about 82.4 grams of phosphoricacid containing about 85 percent by weight of H PO After. being reacted,the novolakcontaining mass was cooled to about. 80 C., neutralized withcaustic solution, washed four times with Water and devolatilized. About5200 grams .of the novolak, dissolved in about 5000 gramsof dioxane, wasplaced in a pressure reactor, into which. was then added about 150 gramsof a percent aqueous-solution of potassium hydroxide (about 1.45 percentby weight, based on the weight of the novolak) and about 6830 grams ofstyrene oxide, which constitutedabout 1.15 moles of theoxide perhydroxyl equivalent of the novolak. The reaction mass was maintained ata temperature of about 115 C. It was then cooled to about 80 ,C. andneutralized with citric acid. The dioxane solvent and unreacted styreneoxide were removed by distillation, after which the remainingpolyalcohol was separately washed four times with hot water 'and driedunder a vacuum. The .cryoscopic molecular weight of the polyalcoholwaspfound to be 1400 and it had an hydroxyl equivalent weight of about230 and a melting point of about 94 C.

Esters prepared in a similar manner to that set forth in Example I withvarious oilfatty: acids provided excellent caustic resistant filmshaving properties; which were determined in the conventional mannerdescribed in Example VI, as indicated in the following table. Thepreparation of .-g en atmosphere for about 6.5 hours at about 230 C.each film.

Table l Sward Caustic Oil fatty acidscharged hardness resistance,

2% no. soln. Viscosity Tack- Gardr .Fatty Weight Cooking Final ofester'in free ner acid of poly- Mols. schedule: acid 70 percent dryingcoloroi Hester alcohol, Percent oil per temp. 0., number xylene timeindried v gins. Type of 01] Weight of by weight alcoholic and time, hrs.of ester solution, air,'hrs. film Air Baked Air Baked fatty acid oil,gms. of oil in equiv. cps. dried 30 min, dried 30 min., i 1 chargeweight 50 0. 150C.

of polyalcohol {A 109 Soya 91 45.5. 0.7 240/6.0 10.7"--. 1,400 1.16 i 527 20 7to14 14 days days .BW." 180.5 Linseed.-- 169.5 48.5. .'0.8240/2.8. 21.0--." 630 1.25 3 '31 45 .do 318 ays j"'C, 220.5 t .d0129.5.-. 37.0 0.5 240/2.8 9.9 6,000 0.66 4 48 418 750 28 1}? ays w S.1);--. 180.5 'Linseed and 169.5 and "48.5 and 0.8and 240/3.0 and 18.9and 870 and 1.00 4 .32 31 1 to 7 10 glycerol. 2.1. 0.6. 0.1. 240/2.0.10.6. 2,270. days wks.

N0'rE.-Glycerol was added after 3 hrs. of esterification with linseedoil fatty acid to react with remaining unreacted fatty acid in order fora low acid numbcrto be obtained without an excessive viscosity'build up.

' liav'iiig acolor, when drie'd,"of about 2 on the Gardner scale. Theairldried coatings, which had a Sward Rocker hardness value of about 22,remained strong and intact after 7 days exposure to a 2.,percent byweight aqueous solution of caustic soda. A film of the ester,-baked for30 ----minutes at 150 C. -(-h-ardness 24),remained clear, strong cudtough after 2 weeks of the same exposure. Similar EXAMPLE III A novolakwas prepared from common phenol with about 0.82 mole of formaldehyde Q61mole: of phenol in the presence of about 1.0 percent of phosphoric acid,based on the weight of the phenol, and water in an amount by weightabout one and one-half times the amount of the phenol. The reaction wasconducted in a Pfaudler reactor at elevated temperatures and pressuresaccording to the procedureset forth1in Example ,I. ..Aftcr beingneutralized, purified and dried, about 500 grams of the novolak wasdissolved in about 500 grams of dioxane to which was added about 14.5grams of an alcoholic solution of potassium hydroxide containing about2.5 grams of KOH. The mixture was placed in a highpressure, rocking-typelaboratory reactor wherein about 404 grams of styrene oxide, whichconstituted'about 0.71 mole of theoxide per hydroxyl equivalent of thenovolak, was added. The mixture was heated for 40 hours at a temperaturein the neighborhood of 110-115 C. At the end of this initial period ofthe reaction, the

8 ing was-conducted in the neighborhood of 110-115' C. for about 48hours. Propylene oxide was employed as the etherification-completingalkylene oxide. It was added in an amount of about 209 grams, whichconstituted about temperature was raised to 150 C. and about 85 grams0.75 mole of propylene oxide per hydroxyl equivalent of ethylene oxide,constituting about 0.40 mole per weight of the novolak. The hard,brittle resinous polynovolak equivalent, was added. Heating wascontinued alcohol obtained had a cryoscopic molecular weight of at atemperature of about 155 C. for an additional five about 1180 and ahydroxyl equivalent weight of 193. hour period, after which the reactionmass was cooled, The yield which was obtained of this polyalcohol wasneutralized with citric acid, devolatilized to free the 10 in the amountof about 863 grams. polyalcohol from solvent and then washed with water.An ester was prepared by heating about 122 grams of There was obtained aresinous polyalcohol having a the polyalcohol together with 128 grams ofsoya oil molecular weight of about 990 and an equivalent weight fattyacids for 8.75 hours at 235 in an inert atmosphere. of about 214 gramsper alcoholic hydroxyl group. About 0.7 of the theoretical amount offatty acid was An ester was prepared with the polyalcohol bycookemployed. After being cooked, the esterified mass had ing togetherabout 129 grams of the polyalcohol with an acid number of 11.7 and aviscosity of about 1600 about 121 grams of soya oil fatty acids under anitrogen centipoises, when dissolved in xylene to obtain a 70 atmospherefor about 7.5 hours at about 230 C. The percent by weight solution. Thecolor of the xylene amount of oil fatty acid used was about 0.7 of theamount solu ion was 13 on the Gardner scale. Air dried and theoreticallyequivalent to the alcohol groups in the baked coatings of the fil hadabout the a ardn ss polyalcohol, The residual acid number of the cookedand caustic resistance as the film obtained in Example HI mass was foundto be about 7.7 and the viscosity of a excepting that the dried film waslighter, having a Gard- 70 percent solution of the ester in xylene (atroom tem- 61 Col r Of 2- 1 perature) was about 1000 centipoises. Thecolor of the E AM VI 70 percent xylene solution was about 13 on theGardner color scale. Films of this ester dried in air to give 1323;3 :52g g222 3 1;g gz ggfig gg g z gx tough lightly colofed coatings having aSward Rocker using novolaks from the common phenol. In order to hardnesswhen dned of abouf 22 and 9 Of about 3 demonstrate by contrast theadvantages to be derived on the Gardner scale. The arr dried coatlngshad good from employment of the common phenol two of the resistance to a2 percent by weight aqueous solution of polyalcohols were Prepared fromsubstinited phenols caustic soda. The film withstood seven daysimmersion The ortho phenyl phenol novolak employed for in such asolution before it disintegrated. A film of the alcohul was madeaccording to the general procedure i baked for 30 minutes at 1500 havinga Sward set forth in Example I. A 0.92 aldehyde to phenol ratiozardriess of remamed clear strong and tough after was used to preparethe novolak with 1 percent by weight weeks of the same exposure ofsodium hydroxide as a catalyst. The solvent used in EXAMPLE 1V preparingthe ortho-phenyl phenol novolak was cmn- When the procedure of ExampleIII was repeated exprised i by dwmgh of w s an equal cepting that 1.0mole of styrene oxide per novolak hyii g t i i droxyl equivalent wasreacted for a 24 hour period at 40 g gg 5 mo i a mo cc at "Z t atemperature of about 120 C. and about 0.1 mole of 3 a on an a me tingpomt of about 128 the ethylene oxide per novolak hydroxyl equivalent wasP f i g al bmyl Phenol nqvolak employed for reacted for 3 additionalhours at about 140 C. and 1.0 oya so 01 was made according to the Samecedure, excepting that a 0.90 aldehyde to phenol ratio percent by weightof the potasslum hydroxide catalyst, with 0 5 r em b ht f ulf a1 basedon the weight of the novolak, was employed, there I h O urflc acl cat wwas obtained a polyalcohol product having a molecular amp g g :52 about133 and weight of about 1290 and a hydroxyl equivalent weight f i fi 7 Ob to be noted that of about 268 grams. Similar results to those ofExample 1 e 3 Ya g S preparle mm Stunted Phenols were I were obtainedwith film coatings consisting of soya ig eslra e m fi g g cqmpanson tomoxie oil fatty acid esters of the polyalcohol. m qommon p eno Pam: arwith regard to appreciably lower molecular weights. It should alsoEXAMPLE V b;: obcsle'vedhthat thtle Eigher etherifying temperatures em 0e ort e novoa -st rene xid The procedure set forth in Example III wasidentically desi rable resinous polyal ohols thar i $51 1? e i gii fyizg repeated excepting that the initial addition of styrene 55temperature between about and C. is employed oxide was only about 202grams (0.35 mole per hyfor the styrene oxide adduct. The results aretabulated droxyl equivalent weight of the novolak) and the heatasfollows.

Table II Novolak Reaction conditions Polyalcohol properties PreparationPercent Heatin schedule Polyanalogous Ratio Percent b we! hg to was areaits? M Type phenol used or phenol of g ggf ggg catalyst solvent Temp,ten igi, 1 12812:- 6 s it?- ratlo novolak equivalent based on based on0., and 0.. ular weight Weight of weight of weight of time, hrs.attained weight (guts) novolak novolak novolak during reaction Common 0.85 706 0.825 722 i 2( i zl i is iii ii: 11;... 3-23 5*: a 123 :2 iOphenylphenol 0192 867 1105 013 50 5:0 23:) iii P-tert.butylphenol. 0.90 698 1.05 0.3 50 160/16.0 240 770 303 p Relatively low molecularweights of polyalcohols from substituted phenols.

ester preparation analogous to that in the preceding examples. Some ofthe properties" of these ester products are set forth in the followingTable III, which also includes details on the preparation of each ester.In several of the preparations glycerol was added nearthe end of theesterification to react with the remaining unreacted oil fatty acids. Inothers an addition of an ethylene oxide ether of a novolak from commonphenol, prepared according to copending application Serial No. 382,852,containing 1.10 moles of ethylene oxide per phenolic unit and having amolecular weight of about 1270 was reacted with the resinous polyalcoholin the indicated manner. It is also to be noted, particularly in bothTables III and IV (which 'follows) and in comparison with other portionsof the "specification, that the esters and the films from esters J 1,I2, Kl-and K2, which were prepared from the polyalcohols made withsubstituted phenols, had generally inferior and lessdesirable'properties than those from polyalcohols made with the commonphenol.

posure. The percentage of gloss retained after this test was 18 percentby G1 and 27 percent by H1, whichis better than isobtainable with mostcommercial varnishes whose gloss retention after such a test is usually;in the neighborhood of 2*l0 percent.

Four of the best quality obtainable commercial resinin-oil sparvarnishes, recommended for outdoor use on wood, were tested incomparison with the coatings, of

master .oils according to the present invention.v These are designatedin Table IV by the Roman numerals in; parentheses.

It is significant that none ofthe improved synthetic drying oils of theinvention were, specially compounded or reinforced for test purposeswith such materials as Table III Oil fatty acid used and finishingtreatment, it any Cooking Viscosity Gardner Poly- Weight schedule,Residual of 70 color alcohol, Ester polytemp., 0., acid percent of 70see Table alcohol Weight Weight Equiv. and number xylene percent IIgIIlS. Kind gms. percent; ratio time, hrs. soln, cps. xyllene so u 109.0 48. l 0. 80 232/10. 5 10. 0 2, 200 15 82. 0 41. 0 0. 60 235] 7. 33 5.4 3, 000 15 101 47. 8 0. 8 240] 5. 0 16. 5 630 13' 3.0 1.5 0.1 230! 3.02.4 1, 000 15 101 47. 8 0.8 240/ 4.0 18. 4 600 15 6.6 0.1 232} 5.0 3.64, 000 15 101 46.0 0.8 238/ 5.0 9.0 800 12 3.0 1.4 0.1 235/ 2.0 1.7 92513 101 43.8 0.8 240] 5.0 10.0 620 15 6.5 0.1 230/ 5.0 2.3 3,300 14 99.544.3 t 0.8 235 2.83 25.2 3, 900 15 99.5 44. 3 0.8 240/ 6.0 15.0 1 15,000 14 118.2 47. 3 7 0. 8 230/ 5. 5 14. 8 980 14 l. 7 0.7 0. 1 230] 2.33 8. l 1, 500 14 1 18 47. 2 0. 8 235] 5. 0 14. 2 4, 600 13 p 80. 5 35.8 0. 5 238] 5. 0 9 15,000 13 112 44. 8 0. 7 240/ 5. 33 12. 9 500 13 598. 5 39. 4 0.8 238l13. 18 9. 3 575 18 72 28.8 0.5 238] 5.0 6.9 3, 60018 106 42. 4 0.8 .240/ 24.0 10. 5 1, 900 l8 79 31.6 0.5 238/ 5.75 9.2630 18 1 Very viscous but no sign of gelation EtOX-N 0v. indicates thedescribed ethylene oxide etherifiednovolak.

Film propertles of some of1the:esters,-prepared as m 50, EXAMPLE VIIdicated in Table III, are detailed in Table IV. The

properties ofthe films were obtained as follows. The films were cast at3 mils wet thickness on 'glass slides using 50 percent solutionsr'of theI ester in petroleum naphtha. The time required by the film to .dry to atack-'2 droxide at room temperature while the condition of the film wasbeing periodically noted. Other such coated slides were immersed in coldwater'for 2 weeks. "Similar tests were made to determine the hardness,alkali and water resistance of similarlyJdespositedfilms. of the.varnish which were bakedat 150 CrfOf minutes.

In addition to what is included in Table IV, 'the weather resistance offilms fromesters G1 and H1 was determined on blocks of vertical grainhemlock carrying 3 coats of the oil film being tested. The coatedblockswere exposed at an angle of to theaground,.facing south, for 14 monthsto the weather 'at Pittsburg, (Balifornia. -The-Glossi-ness of-thecoatings was measured,

and computed in the percent of the value before ex- A novolak having amolecular weight of about 800 was prepared in a pressure vessel byreacting, at. 150 C. for one hour, about 8235 grams of common phenolwith about 5900 grams of 37 percent formalin (to provide an aldehyde tophenolratio of about 0.82) in the presence of about 8590 milliliters ofsupplementary water and about 82.4 grams of phosphoric acid containingabout 85..percent by weight of H PO After being reacted, thenovolak-containing mass was cooled to about C., neutralized with causticsolution, washed four times with distilled water and. devolatilized.About. 3395 grams of the novolak, dissolved in about 2 500 gramofadioxane, was placed in a pressure reactor. About 34 grams-of a 50percent aqueous solution of potassium hydroxide and about 3880 grams ofstyrene oxide were then added to the reactor. The reaction mass wasmaintained at a temperature oftabout" C. fortaxreactionperiod ofabout24. hours. :About 728-grams of-phenyl glycidyl ether was then introducedinto the reacted mass and heating continued for an additional four hoursata temperature of about C. in order to scavenge-the unreacted hydroxylgroups in the already etherified polyalcohol. The reaction mass was thencooled to about 80 C. and neutralized with about 32 gramfsiofi citi'igTable IV Air dried samples Baked 30 min/150 C. 7

Flexi- Ester Tack- Gardner bility free color of Hard- Water soaking 2percent NaOH Hard- Water soaking 2 percent NaOH time, dried ness soakingness soaking hrs. film 123.... 1. 75 3H-P Very slight-24 hrs. TH-P 14days-Hard and Hazy OK on clear. hardening. 134.... 1. 33. 5 33-1 Veryslight-48 hrs. 7H-P .do Hazy OK on hardening. FL... 1. 13 4 411-1 24hrs.Slight haze- 7H-P d0 Med. hard 48 hrs. hazy and soft. F2.- 1.0 4411-1 48ll1rsd-Clear and 7H-P do ar EL--. 1. 25 g 5 3H]? 4 days-Med.hard GH-P 4 deys0lear, med.

and opaque. hard-2 mos. same. 112.... 0.75 4 14 days-Tough and 24hrs-Strong and 42$ 2 wks.-Str0ng, 2 wks.-Clear, strong,

strong. hard-Soft in 2 wks. hard. hard. H3.-.. 0. 50 4 54S 24hrs-Brittle 24 hrs.-Brittle 588 7 %a ytstTHard and 24thrs.hClear, strongr1 0. oug 114.... 0.75 4 348 2 wks.Strong and 24 hrs-Clear, hard 40$ 2wks.Strong, 2 wire-Clear, strong tough but softer. strgoug-Softer in 2tough. tough.

w s. 0.25 7 485 24 hrs-Brittle 24 hrs-Brittle 56S 24 hrs.Brittle 24hrs-Brittle No good. 0. 07.. 9 56S No good do 785 do d0 1. 50 3 343...do 24 brag-Brittle and 388 do do No good.

wea 1.00 3 548 .....do 24 hrs.--Soft weak-1 603 ..do 24 hrs.So1't wk.disintegrated. 1.07 18$ 2 wks.-S0it and 2hrs.Disintegrated.. S2wks.-Hard, tough. 3hrs.Disintegrated.

wea 1.07 438 1 wk.Hazy, strong- 24 hrs.-Cloudy, ML. 468 do 7 daysHCIear,hard 1 on 1.07 24$ 2 wks.-Soft clear--. 24 hasr-weak and 368 .do 7dayE-Very weak-..

so 1. 00 168 .do 3 hrs.-Wrlnkled24 16$ 7 days-Very soft.

, hrs. disintegrated.

P-pencil hardness; S-Sward hardness.

acid. The dioxane solvent was removed by distillation about 24. Anotherfilm of the ester, baked on a glass and the remaining polyalcohol waswashed with four two-gallon volumes of distilled water and dried under avacuum. The cryoscopic molecular weight of the polyalcohol was found tobe 1490 and it had an hydroxyl equivalent weight of 230.

An ester was prepared by heating about 107 grams of the polyalcohol withabout 93 grams of soya oil fatty acids under a nitrogen atmosphere forabout 5.3 hours at a temperature of about 240 C. The amount of fattyacid usedwas 0.7 of the amount theoretically equivalent to the alcoholgroups in the polyalcohol. The residual acid number of the prepared masswas found to be about 9.5 and the viscosity of a 70 percent solution ofthe ester in xylene (at room temperature) was about 1100 centipoises.With addition of conventional metallic driers, a film of the oil, whichhad been cast on a glass plate to have a thickness of about 3 mils,dried to a tack-free state in air at room temperature within 2.75 hours.The color of the dried film on the Gardner scale plate for 30 minutes at150 C. had a Sward hardness of about 26. Both films had excellentresistance to caustic alkali solutions.

EXAMPLE VIII Results similar to those in the foregoing Examples III, IV,V and VII may be obtained when hydroxy propylene oxide is employed asthe more reactive organic oxide to complete the etherification of thepolyalcohol material following the initial etherification with styreneoxide.

EXAMPLE IX Various styrene oxide-containing polyalcohols, preparedaccording to the general procedures set forth in the first sevenexamples, were obtained under conditions and had properties as aredetailed in and by the following table. All of the polyalcohols involvedwere prepared from a similar novolak condensate as that employed in was.The air dried film had a Sward hardness of Example VI.

Table V Catalyst Oxide component Reaction conditions Identifl- DioxaneCryo- Hydrox cation of Novolak solvent Weight Percent Ratio, Max. scopicweight Melting resin and weight, weight, of 50 by Weight moles Tomp.,tgmo, weight, equ1va ppint, polyalcohol gins. gms. Kind percent weightKind; of oxides, oxide 0., and 0., moleclent, C.

aq. sol. based on grams equiv. of time. hrs. attained ular grams M 1gms. novolak novolak during 1 reaction L 1,710 3,855 NaOH 77.1 0.5 :52$4 219 1,205 101 82 e N 1,500 4,800 KOH 150 1.0 {2f 33 3 1134 33, 1,305150 .sa

. O P 6,745 5,000 KOH 140 1.04 iggg 8 g; 1,330 189 so a R a 500 500 KOH5.0 0.5 g; 31g $24 2 9 000 214 o s. 5,500 5,500 KOH 1.00 '22 2% iggsf gg 1,035 234 05 i St (styrene oxide), Et (ethylene oxide).

Table VI 011 fatty acids charged Sward hard- Caustic resistance'Viscosness 1 Cooking. Final ity of Time Gard- Y- ght 7 schedule: acidester reqd ner Fatty alcohol of poly- Percent Moles temp, numin 70 todry color t 109 01, by oil 0., and her percent to of Baked ester Tablegrams Type of Weight weight per time, of xylene touch dried A 1r 30min.Baked g min.,

) oil fatty of oil, of oil alcohrs. ester soluin air film dne at Airdried 150 0.

acid grams in holic tion, 150

charge equiv. cps. I 0.

L 111 55. 0. 7 239/6. 00 2. l 600 1. 1 2O 12 1 hr. t0 1' d9... 1 hr. to1 da. N 112 56.0 0.7 240/3. 75 3. 7 620 0. 75 2 9 9 1 dc. to 7 da 1 dc.to 7da.

- N 208. 5 59. 5 0.8 230/3. 00 7. 0 700 0.72 2 16 13 1 da. to 7 da 1 da.to 7 da.

- N 167. 5 48. 0 0. 5 240/1."25 4. 9 2,300 0. 67 3 27 43 1 da. to 7dc... 1 da. to 7 da.

P 190 54. 3 0. 8 240l2. 83 ll. 0 2, 400 1. 83 2 29 25 1 da. t0 7 (1a..11 (la. to 14 da P 513 42. 7 0. 6 240/2. 18 6. 3 4, 000 '0. 83 3 42 1(13.. to 7 da 21 (la. 1:0 28 da R 129 Soya 121 48. 4 0. 7 230/7. 5 0 7.7 1. 000 4. 3 22 24 1 da. to 7 da.. 14 da. 8 107. 5 do. 92.5 46.3 0.7240/3. 00 0.6 3, 000 2. 67 4 28 31 1 da. to 7 da. 7 da. to 14 da 1Hr.hours, da.days.

Various oil fatty acid esters made from the polyalcohols prepared as setforth in Table V provided excellent caustic resistant films. This isindicated in the above table, which also includes details relating tothe preparation of each film.

EXAMPLE X Various synthetic drying oils were prepared by blending, indiffering proportions, an ester of a polyalcohol etherified solely withstyrene oxide (the polyalcohol being similar to that obtained in Example11) and a 0.5 mole linseed oil fatty acid ester of a similarly preparedpoly- ;alcohol excepting that it was etherified solely with ethyleneoxide to contain about 1.0 mole of the reacted oxide per phenolic unitin the novolak. Before being esterified, 3 viscosity f a it had amelting point of about 64 C., a molecular weight of about 1253, and anequivalent weight of 152 grams per alcoholic hydroxyl. Details on thepreparation of the mixtures and their film properties are given in thefollowing Table VII, which includes the transient color changes 40 ofthe films on the Gardner color scale from their applied to their driedconditions. An exposure of 25 to 30 hours in a standard Fadeometertesting apparatus was utilized to determine the exposure color changesof the films as measured by a Photovolt instrument using a 45.

white tile as standard. The color changes in the Fadeometer testgenerally occurred within the first few hours of exposure after which nofurther appreciable change in color was observed during testing foradditional periads of as long as several weeks.

following Table VIII. All of the tests were made in accordance withdetails of the preceding examples.

Table VIII Ester"; X Y Z Weight percent of polyalco ol 8.0 21.0 38.2.etherificd with EtOx in oil.

Weightpcrcent of polyalcoiol 53.0 36:0 15.7.

ctherified with StOx in oil. Weight percent linseed oil fatty 39.0 42:240.1.

acidin oil. M01 ratio of etherlfied EtOx 0.2 0.5 0.8.

roups in oil. Moi ratio of ctherificd StOx 0.8 0.5 0.2.

groups in oil. Ratio of equiv. of linseed oil 0.5 0.5 0.5

fatty acid per available also holic hydroxy] in polyalcosol. inal acidnumbenm 7.1 4.0 1.5.

2,400 2,700 1,800. xylene soln, cps. Tack-free time, minutes 40 40. 45.Gaf iridner color change of drying. l-6-3 1-4-3 1-3-2.

in. Initial Fadeometer color air 83 89 02.

dried film. Final Fadeometer color air 71 77 78.

d ied film. v lnfiitiial Fadeometer color baked 65 68 78.

m. Fifinlal Fadeometer color baked 75 79.

m. Sward hardness, air dried film 42 38 33. Sward hardness, baked film33. 27. 21. 3 percent aq. NaOH resistance 2-5 days... 1 day 1 day.

of air dried film. 3 percent aq. aOH resistance Unaffected Unafi'ected5-8 days.

of baked lm. after 12 after 12 days. days.

Nori:.StOx-styrene oxide etherilied novolak, EtOxethylcnc oxideetherified novolak.

Table VII Composition by wt. Gardner Fadeometer exposure color Swardhardness Caustic resistance, 3 percent Ratio of. percent of oils colorchange change NaOH soln equiv. of Tackin oil film Ester StOx; EtOx freeon drying: mixture in esterfied time, applied- Air Dry Baked Bakedadducts StOx oil EtOx oil minute dgying- Air dry Baked Alr'dry (30 min.at

rie

Initial Final Initial Final MA. 100:00 100 0 25 2-55 88 75 63 72 50 45Unaffected Unaffected. MB :20 84. 2 15. 8 35 2-5-5 88 75 68 75 40 MO65:35 71.1 28. 9 36 2-5-5 88 75 72 76 37 D0. MD 50:50 57.0 43. 0'- 452-5-4 76 73 76 37 D0. ME 35:65 41. 8 58. 2 60 2-5-3 91 75 74 76 30 5-8days MEX.-- 20:80 24. 9 75.1 60 1-4-2 93 78 75 78 28 4-5 days. MG-.-.10:90 12. 9 87. 1 60 1-3-2 93 77 77 76 25 2-4 days. I MEN- 0:100 0 10060 1-1-1 77 79 78 26 1-3 days.

StOx-styrene oxide etherified novolak ester. EtOx-ethylcne oxideetheritied uovolak ester.

EXAMPLE XI Various ester oils were prepared according to the: generalprocedure of the foregoing examples by esterifying mixtures of thestyrene oxide etherified polyalcohol and an ethylene oxide etherifiedpolyalcohol each of the polyalcohols was similar to those employed inthe ester oils "o'fExample VIII. Details on the preparation of theesters and on their film properties are included in the Since certainchanges and modifications can be readily entered into in the practice ofthe present invention without substantially departing from its intendedspirit and scope, it is to be fully understood that all of the foregoingdescription and specification. be interpreted as being merelyillustrative ofpreferr'ed embodiments'pf )75 the invention which is notto be construed asbeiiigliim ited or restricted thereby excepting as itis set forth and defined in the appended claims.

What is claimed is:

1. An esterification product of (1) a resinous polyalcohol consisting ofthe etherified product of a phenolformaldehyde novolak which is thereaction product of phenol and formaldehyde and which has from three toten phenolic units per molecule in which at least about 70 percent ofthe phenolic hydroxide groups originally present in the molecule areetherified with from 0.2 to 1.2 moles per each phenolic unit of styreneoxide and (2) carboxylic acids in an amount to provide at least about0.2 to 1.0 carboxyl groups per alcoholic hydroxyl of said resinouspolyalcohol, at least about 60 percent of the carboxyl groups beingfurnished by fatty acids having drying characteristics said fatty acidsbeing monomeric acids selected from the group consisting of thoseobtained by saponification of drying oils, semi-drying oils, andmixtures thereof.

2. The product of claim 1 wherein substantially all of the phenolichydroxide groups originally present in the novolak molecule areetherified with styrene oxide.

3. An esterification product of (1) a resinous polyalcohol consisting ofthe etherified product of (a) a phenolformaldehyde novolak which is thereaction product of phenol and formaldehyde and which has from three toten phenolic units per molecule with (b) from 0.7 to 1.2 moles per eachphenolic unit of styrene oxide and with (c) not more than about 1.0 moleper each phenolic unit of a relatively more reactive organic oxideselected from the group of organic epoxides consisting of alkyleneoxides containing from 2 to 4 carbon atoms in their molecule; hydroxyalkylene oxides containing from 3 to 5 carbon atoms in their molecule;and aryl glycidyl ethers, in which etherified product at least about 7-0percent of the phenolic hydroxy groups originally present in the novolakare etherified and (2) carboxylic acids in an amount to provide at leastabout 0.2 to 1.0 carboxyl of said resinous polyalcohol, at least about60 percent of the carboxyl groups being furnished by fatty acids havingdrying characteristics said fatty acids being monomeric acids selectedfrom the group consisting of those obtained by saponification of dryingoils, semi-drying oils, and mixtures thereof.

4. The product of claim 3 wherein substantially all of the phenolichydroxide groups originally present in the novolak molecule areetherified with at least about 0.8 mole of styrene oxide per phenolicunit.

5. The product of claim 3 wherein the polyalcohol has not more thanabout 0.5 mole of styrene oxide and a total of not more than about 1.25moles of both oxides per phenolic unit and in which substantially all ofthe phenolic hydroxyl groups originally present in the novolak areetherified. I

6. The product of claim 3 wherein the relatively more reactive organicoxide is ethylene oxide.

7. The product of claim 3 wherein the relatively more reactive oxide isphenyl glycidyl ether.

8. The product of claim 3 wherein essentially all of the esterifyingacids have drying characteristics.

9. The product of claim 3 wherein the amount of carboxylic acids used inthe esterification reaction provides in the neighborhood of about 0.5carboxyl groups per alcoholic hydroxyl of the resinous polyalcohol.

10. An esterification product of (1) a mixture of resinous polyalcoholsconsisting of the etherified product of (a) a phenol-formaldehydenovolak which is the reaction product of phenol and formaldehyde andwhich has from three to ten phenolic units per molecule with (b) from0.7 to 1.2 moles per each phenolic unit of styrene oxide in which atleast about 70 percent of the phenolic hydroxy groups originally presentin the novolak are etherified and the etherified product of a (c)novolak which is thereaction ,prdductjof. phenol and formaldehyde andwhich has from three to ten phenolic units per molecule with (d) notmore than about 1.25 moles of a relatively more reactive organic oxideselected from the group of organic epoxides consisting of alkyleneoxides containing from 2 to 4 carbon atoms in their molecule; hydroxyalkylene oxides containing from 3 to 5 carbon atoms in their moleculeand aryl glycidyl ethers in which at least about 70 percent of thephenolic hydroxy groups originally present in the novolak are etherifiedand (2) carboxylic acids in an amount to provide between about 0.2 and1.0 carboxyl groups per alcoholic hydroxide of said resinouspolyalcohols, at least about 60 percent of the carboxyl groups beingfurnished by fatty acids having drying characteristics said fatty acidsbeing monomeric acids selected from the group consisting of thoseobtained by saponification of drying oils, semi-drying oils, andmixtures thereof, wherein the proportion of etherified styrene oxideadducts the sum total of etherified oxide adducts which are present inthe esterified product is between about 25 and mol percent.

11. The product of claim 10 wherein the carboxylic acids are in anamount to provide in the neighborhood of about 0.5 carboxyl groups peralcoholic hydroxide of said resinous polyalcohols.

12. The product of claim 10 wherein the relatively more reactive organicoxide is ethylene oxide.

13. An esterification product consisting of a mixture of (1) anesterification product of (a) a resinous polyalcohol consisting of theetherified product of a phenol-formaldehyde novolak which is thereaction product of phenol and formaldehyde and which has from three toten phenolic units per molecule with from 0.7 to 1.2 moles of styreneoxide per each phenolic unit in which at least about 70 percent of thephenolic hydroxy groups of originally present in the novolak areetherified and (b) carboxylic acids in an amount to provide betweenabout 0.2 and 1.0 carboxyl groups per alcoholic hydroxide of saidstyrene oxide-etherified resinous polyalcohol, at least about 60 percentof the carboxyl groups being furnished by fatty acids having dryingcharacteristics said fatty acids being monomeric acids selected from thegroup consisting of those obtained by saponification of drying oils,semi-drying oils, and mixtures thereof and (2) an esterification productof (c) a resinous polyalcohol consisting of the etherified product of anovolak which is the reaction product of phenol and formaldehyde andwhich has from three to ten phenolic units per molecule with not morethan about 1.25 moles of ethylene oxide per each phenolic unit in whichat least about 70 percent of the phenolic hydroxy groups originallypresent in the novolak are etherified and (d) carboxylic acids in anamount to provide between about 0.2 and 1.0 carboxyl groups peralcoholic hydroxide of said ethylene oxide-etherified resinouspolyalcohol, at least about 60 percent of the carboxyl groups beingfurnished by fatty acids having drying characteristics, said fatty acidsbeing monomeric acids selected from the group consisting of thoseobtained by saponification of drying oils, semi-drying oils, andmixtures thereof, wherein the proportion of etherified styrene oxideadducts to the sum total of etherified oxide adducts which are presentin such a mixture is between about 25 and 100, mol percent.

14. The product of claim 13 wherein the carboxylic acids are in anamount to provide in the neighborhood of about 0.5 carboxyl groups peralcoholic hydroxide of each resinous polyalcohol.

References Cited in the file of this patent UNITED STATES PATENTS2,422,637 Thomas June 17, 1947 2,499,365 De Groote et al Mar. 7, 19502,581,379 De Grootc et al. Jan. 8, 1952 2,695,894 DAlelio Nov. 30, 1954

1. AN ESTERIFICATION PRODUCT OF (1) A RESINOUS POLYALCOHOL CONSISTING OFTHE ETHERFIED PRODUCT OF A PHENOLFORMALDEHYDE NOVALAK WHICH IS THEREACTION PRODUCT OF PHENOL AND FORMALDEHYDE AND WHICH HAS FROM THREE TOTEN PHENOLIC UNITS PER MOLECULE IN WHICH AT LEAST ABOUT 70 PERCENT OFTHE PHENOLIC HYDROXIDE GROUPS ORIGNINALLY PRESENT IN THE MOLECULE AREETHERIFIED WITH FROM 0.2 TO 1.2 MOLES PER EACH PHENOLIC UNIT OF STYRENEOXIDE AND (2) CARBOXYLIC ACIDS IN AN AMOUNT TO PROVIDE AT LEAST ABOUT0.2 TO 1.0 CARBOXYL GROUPS PER ALCOHOLIC HYDROXYL OF SAID RESINOUSPOLYALCOHOL, AT LEAST ABOUT 60 PERCENT OF THE CARBOXYL GROUPS BEINGFURNISHED BY FATTY ACIDS HAVING DRYING CHARACTERISTICS SAID FATTY ACIDSBEING MONOMERIC ACIDS SELECTED FROM THE GROUP CONSISTING OF THOSEOBTAINED BY SAPONIFICATION OF DRYING OILS, SEMI-DRYING OILS, ANDMIXTURES THEREOF.